CN100404487C - Process for the isomerisation of a cyclohexenyl alkyl or alkenyl ketone - Google Patents

Process for the isomerisation of a cyclohexenyl alkyl or alkenyl ketone Download PDF

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CN100404487C
CN100404487C CNB2004800364036A CN200480036403A CN100404487C CN 100404487 C CN100404487 C CN 100404487C CN B2004800364036 A CNB2004800364036 A CN B2004800364036A CN 200480036403 A CN200480036403 A CN 200480036403A CN 100404487 C CN100404487 C CN 100404487C
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ruthenium
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diene
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CN1890204A (en
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丹尼斯·雅各比
贝萨阿·内法
克里斯蒂安·沙皮伊
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    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
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Abstract

The present invention relates to a process for the carbon-carbon double bond isomerisation of a 2-alkyl-cyclohex-3-enyl alkyl or alkenyl ketone into a mixture comprising the corresponding 2-alkyl-cyclohex-2-enyl ketones and the corresponding 2-alkylene-cyclohexyl ketones, using as catalyst a ruthenium complex obtainable by the reaction of an appropriate ruthenium organometallic precursor and an acid.

Description

The isomerization method of cyclohexenyl alkyl or alkenyl ketone
Technical field
The present invention relates to the organic synthesis field.Or rather, it provides a kind of 2-alkyl-hexamethylene-3-thiazolinyl alkyl or alkenyl ketone isomery has been turned to the method that contains the corresponding 2-alkyl-hexamethylene-2-alkenyl ketone and the mixture of corresponding 2-alkylidene group-pimelinketone, and this method uses the complex compound that obtains by suitable ruthenium Organometallic precursor and acid-respons as catalyzer.
Background technology
The compound of formula as follows (II) or (II ') can be used as perfuming component or as the structure skeleton structure starting raw material of complex compound more.
The disclosed method for preparing above-claimed cpd is general chronic and cost an arm and a leg in the prior art.And every kind of described method can only obtain one or another kind of in the above-claimed cpd.Therefore, must implement two independently processes, waste the time significantly in order to obtain above-mentioned compound those skilled in the art.
Therefore press for by simple and effective isomerization method and obtain above-claimed cpd, its starting raw material is the material that obtains easily and can obtains compound (II) simultaneously and (II ').
As far as we know, there is not report in the prior art about the isomerization method of the compound that can directly obtain formula (II) and (II ') simultaneously.
Summary of the invention
In order to solve the above problems, the invention provides a kind of method the substrate isomery shown in the formula (I) is turned to the mixture that contains the compound shown in the compound shown at least a formula (II) and at least a formula (II '),
Figure C20048003640300071
Each R wherein 1Simultaneously or represent hydrogen atom or methyl group and R independently 2Represent the C of hydrogen atom, straight or branched 1-4Alkyl or C 2-5The 1-alkenyl group;
R wherein 1And R 2Have with above-mentioned shown in identical implication;
Described method is carried out in non-coordination or weak coordinate medium, under the condition that exists of inert environments catalyst neutralisation, and above-mentioned catalyzer is to be obtained by following substance reaction in non-coordination or weak coordinate medium He in the inert environments:
A) formula [ruthenium (diene) (allyl group) 2], [ruthenium (dialkylene) 2], the ruthenium precursor of [ruthenium (tetraene) (alkene)] or [ruthenium (diene) (triolefin)]; With
B) protonic acid of formula HX, wherein X is weak coordination or non-coordinate negatively charged ion; Or formula B (R 3) 3Lewis acid, R wherein 3Represent fluoride or by 1 to 5 group such as halogen atom or methyl or CF 3The phenyl group that group replaces arbitrarily, perhaps formula FeX 3, FeX 2, AgX, AlY 3, FeY 3, FeY 2, SnY 2, SnY 4, AgY, AgY 2, SbY 5, AsY 5Or PY 5Lewis acid, X is to be the fluorine or chlorine atom as top defined group and Y;
The mol ratio of acid/ruthenium is 0.3 to 3.1.
Contain another kind of compound in the mixture that is obtained by isomerization method of the present invention, it is useful that this compound is mentioned, and it is the ketenes shown in the following formula (III):
Figure C20048003640300081
R wherein 1And R 2Has the identical meanings shown in the formula (I).Described compound (III) is the possible component that obtains when isomerization finishes in the mixture, in fact, the applicant has been found that the formation of described compound (III) depends on concrete test conditions, the ratio that particularly depends on Ru/ acid, the temperature and the time length of reaction, perhaps depend on used catalyzer and concentration thereof.Usually, compound (III) in final mixture shared weight less than 2%.According to a preferred embodiment of the invention, the compound that does not contain described formula (III) in the final mixture.
According to a preferred embodiment of the invention, substrate is as shown in the formula the compound shown in (IV)
Figure C20048003640300082
R wherein 1And R 2Has the identical implication shown in the formula (I), preferred R 1Represent hydrogen atom and R 2Represent hydrogen atom or methyl or CH=CHCH 3Group; And
The compound that contains corresponding formula V and (V ') in the mixture that obtains
Figure C20048003640300083
R wherein 1And R 2Has the identical implication shown in the formula (IV).
In described embodiment, the possible component of said mixture is as shown in the formula shown in (VI)
Figure C20048003640300091
R wherein 1And R 2Has the identical implication shown in the formula (VI).
In addition, except specific embodiment, very important what also should be mentioned is that the compound of formula (I) and corresponding compounds (II) or (II ') can be the forms of optically active form, and especially, compound (I), (II) or (II ') can be forms shown in the following formula
R wherein 1And R 2Have identical implication and the asterisk shown in above-mentioned and be meant that described compound is the form of optically active form.
The object lesson of compound (I) opticity is (2E)-1-[(1S, 2R)-2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl]-2-butylene-1-ketone, (2E)-1-[(1S, 2S)-2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl]-2-butylene-1-ketone, 1-[(1S, 2R)-2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl]-1-ethyl ketone or 1-[(1S, 2S)-2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl]-the 1-ethyl ketone.
Catalyzer is the key element of method of the present invention.Aforesaid catalyzer is to react in non-coordination or weak coordinate medium and in the inert environments by organo-metallic ruthenium precursor and specific Lewis acid or protonic acid to obtain.
As the non-limitative example of appropriate ruthenium precursor, can enumerate general formula [ruthenium (diene) (allyl group) 2] compound, wherein " diene " representative contains the C of two carbon-to-carbon double bonds 4-C 20, preferred C 4-C 10The alkyl gene, for example COD (ring hot-1,5-diene) or NBD (norbornadiene), or also have heptan-1,4-diene, and " allyl group " representative contains C=C-C-or the segmental C of C=C-C 3-C 20, preferred C 3-C 10Hydrocarbyl group, 2-allyl group or the 2-methylallyl (reference of being quoted referring to for example J.-P.Genet et al. for example; M.O.Albers et al.Inorganic Synth. 1989, 26,249; R.R.Schrock et al.J.Chem.Soc.Dalton Trans. 1974, 951).
Other suitable ruthenium complexs comprise [ruthenium (dialkylene) 2] compound of type, wherein " dialkylene " representative contains a carbon-to-carbon double bond and a C=C-C -, C=C-C or C=C-O -Segmental C 4-C 20, preferred C 4-C 15Hydrocarbyl group, for example pentadienyl, cyclopentadienyl, substituted cyclopentadienyl (as pentamethyl--cyclopentadienyl), 2,4-dimethyl pentadiene base, 2,3,4-trimethylammonium pentadienyl, 2,4-two (tertiary butyl)-pentadienyl or also have 2,4-dimethyl-1-oxa-pentadienyl (referring to, R.D.Ernst et al.J.Organometallic Chem. for example 1991, 402,17; L.Stahl et al.Organometallic, 1983, 2,1229; T.Schmidt et al.J.Chem.Soc.Chem.Commun. 1991, 1427; T.D.Newbound et al.Organometallics, 1990, 9,2962), or also have 2,5-cyclooctadiene base or 2,5-cycloheptadiene base (referring to, P.Pertici et al.J.Chem.Soc.Dalton Trans. for example 1980, 1961).
Also having other ruthenium complexs that are fit to is ruthenium complexs of formula [ruthenium (diene) (triolefin)], and wherein " triolefin " representative contains the C of three carbon-to-carbon double bonds 7-C 20, preferred C 7-C 12The alkyl gene, for example ring is hot-1,3,5-triolefin (COT), benzene or substituted benzene is hexamethyl-benzene for example.Preferred triolefin is COT.
Another suitable ruthenium complex is the ruthenium complex of formula [ruthenium (tetraene) (alkene)], and wherein " tetraene " representative contains the C of four carbon-to-carbon double bonds 8-C 20, preferred C 8-C 12Hydrocarbyl group, for example ring is hot-1,3,5,7-tetraene, and " alkene " representative contains the C of a carbon-to-carbon double bond 2-C 10, preferred C 4-C 8Hydrocarbyl group, for example cyclooctene or tetrahydrobenzene.
According to the preferred embodiment of the invention, what be used as the Ru precursor here is the compound of following formula: [Ru (COD) (2-methylallyl) 2], [Ru (COD) (COT)], [Ru (2,4-dimethyl pentadiene base) 2] (for example L.Stahl et al. or T.D.Newbound et al. are quoted reference) or [Ru (2,4-dimethyl-1-oxa-pentadienyl) 2] complex compound (for example T.Schmidt etc. quoted reference).[Ru (COD) (2-methylallyl) 2] preparation at first by J.Powell etc. at J.Chem.Soc. (A), 1968, disclosed in 159, confirm that from practical angle this method is quite easily.
Will use acid in the process of preparation catalyzer, described acid is assert to make the ruthenium precursor cationization.
The type of employed first kind of suitable acid is the acid of proton type in Preparation of Catalyst.Described protonic acid must have weak coordination or non-coordinate negatively charged ion." weak coordination or non-coordinate negatively charged ion " expressed here implication is with catalyzer the negatively charged ion significantly react to each other not to take place under reaction conditions, and the technician in catalysis field can understand this implication well.In other words, weak coordination or non-coordinate negatively charged ion are a kind of like this negatively charged ion, it does not cooperate fully with the Ru center of catalyzer or its ligand stability constant less than the ligand stability constant of the substrate shown in the formula (I).
The non-limitative example that is suitable for preparing the protonic acid of catalyzer is the acid of formula HX, and wherein X is ClO 4 -, R 4SO 3 -, R wherein 4Be chlorine or fluorine atom or C 1-C 8Fluoro-alkyl or fluorinated aryl group, BF 4 -, PF 6 -, SbCl 6 -, AsCl 6 -, SbF 6 -, AsF 6 -Or BR 4 -, wherein the R representative is by 1 to 5 group such as halogen atom or methyl or CF 3The phenyl group that group replaces arbitrarily.
According to a preferred embodiment of the invention, weak coordination or non-coordinate negatively charged ion are BF 4 -, PF 6 -, C 6F 5SO 3 -, CF 3SO 3 -Or also have B[3,5-(CF 3) 2C 6H 4] 4 -, more preferably BF 4 -
Can also use the form (HBF for example of the corresponding etherate of above-mentioned protonic acid 4R 5 2O, R 5Be C 1-C 5Hydrocarbyl group is as C 2H 5Or C 4H 9).These etherates are that commercially available commodity or they can be by in containing the solvent of dialkyl ether, and the mixture of methylene dichloride and diethyl ether for example obtains AgX and HCl reaction.As silver nitride precipitation, it provides sour etherate solution, and this solution can be used for the reaction with ruthenium precursor according to the present invention.
The type of employed second kind of suitable acid is the acid of Louis's type in the preparation catalyzer.The appropriate example of this acid is FeCl 3, AlCl 3, SbF 5, AsF 5Or PF 5, AgF, Fe (CF 3SO 3) 3, AgBF 4, SnCl 2, BF 3Or BMe 3
Described acid can be anhydrous form, also can be the form of hydrate for wherein number acid perhaps.And, the derivative of boron or aluminium, particularly BF 3Can be with any the form in the adducts of it and ether or carboxylic acid, as R 6 2O or R 7COOH, wherein R 6Be C 1-C 5Alkyl group and R 7Be C 1-C 20Alkyl group.According to a particular embodiment of the invention, preferably Lewis acid is BF 3Or BF 3With Et 2O, Bu 2The adducts of O or AcOH.
According to above-mentioned, in Preparation of catalysts, acid and ruthenium precursor are to be 0.3 to 3.1 to react with mol ratio.Described according to a preferred embodiment of the invention ratio is about 0.5 to 2.
In order not reduce the validity of catalyzer, also should in non-coordination or weak coordinate solvent He under the inert environments, prepare catalyzer.The implication that " non-coordination or weak coordinate solvent " expresses is can not make the obvious inactivation of catalyzer and can make substrate and the interactional solvent of catalyzer, and the technician in catalysis field can understand this implication well.In other words, weak coordination or non-coordinate solvent are a kind of like this solvents, it does not cooperate fully with the Ru center of catalyzer or its ligand stability constant less than the ligand stability constant of the substrate shown in the formula (I).
Usually, any solvent that is inertia and can dissolves substrate and catalyzer under experiment condition all is very suitable solvent.In the particular embodiment of the present invention, above-mentioned solvent is the substrate shown in chlorating hydrocarbon, saturated or undersaturated hydrocarbon, ether, ester, carboxylic acid, weak coordinate ketone (steric hindrance ketone) or the formula (I), or their mixture.The object lesson of above-mentioned solvent is methylene dichloride, heptane, octane, dibutyl ether, butylacetate, acetate, tertiary amyl-methyl ether, diisobutyl acetone or the compound of formula (IV) as defined above.
The implication that " inert environments " expresses is a kind of like this environment, and it and catalyzer do not react, and particularly the oxygen content of this environment is lower than 200ppm, and preferably are no more than 100ppm.
Known to us, the catalyzer that obtains according to aforesaid method (and the acid in this method be Lewis acid) as defined above is new compound.Described catalyzer also is a target compound of the present invention.Preferred Lewis acid is BF 3, BF 3Et 2O, BF 3Bu 2O or BF 3(AcOH) 2Preferred ruthenium precursor is following complex compound: [Ru (COD) (2-methylallyl) 2], [Ru (COD) (COT)], [Ru (2,4-dimethyl pentadiene base) 2] or [Ru (2,4-dimethyl-1-oxa-pentadienyl) 2], and preferred especially [Ru (COD) (2-methylallyl) 2].
Method of the present invention also should be carried out in non-coordination or weak coordinate solvent He in the inert environments.Described solvent and the environment as above formation of surface catalysis agent are defined the same.
Employed catalyzer is generally 0.01 to 2 mole of % with respect to the consumption of substrate in the process of the present invention.In the preferred embodiment of method of the present invention, used catalyst concentration is about 0.05 to 1 mole of %.More preferably, the content of catalyzer is about 0.1 to 0.4 mole of %.Use excessive catalyzer can cause in the mixture that obtains, occurring the compound of formula (III).
The temperature that process of the present invention can be carried out be 60 ℃ to the temperature range between the reflux temperature of solvent or substrate.Preferred 60 ℃ to 180 ℃ of temperature range, more preferably 110 ℃ to 165 ℃, and be preferably 110 ℃ to 150 ℃.Certainly, those skilled in the art also can select preferred temperature as the fusing point of starting raw material and final product and solvent and the function of boiling point as.
Yet must be noted that when the process temperature is 150 ℃ to 180 ℃, can contain the compound of a considerable amount of formulas (III) in the mixture that when reaction finishes, obtains, keep if particularly after the conversion of no longer observing substrate, also this is reflected under the said temperature.
Now describe the present invention in further detail by the following examples, abbreviation wherein has the general implication of this area, temperature with degree centigrade (℃) represent.
Embodiment
Embodiment 1
1-in the presence of the catalyzer that obtains with protonic acid (2,6,6-trimethylammonium-3-tetrahydrobenzene -1-yl)-isomerization of 1-ethyl ketone
20 ℃, under nitrogen protection, to (4.52 moles of trans 1-(2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl)-1-ethyl ketone; Trans/cis=94/5 is to 99/1, purity 〉=99%) in stir and add HBF 4OEt 2(the HBF of 4.54 mmoles 4) and then add [Ru (COD) (methylallyl) 2] (4.54 mmole).The solution that obtains is heated to 130 ℃ and keep this temperature to stir 30 minutes under nitrogen protection.Afterwards, the mixture that obtains is cooled to 20 ℃ of mixtures that contain following material that can obtain (calculate with the final mixture weight percent, obtain) by gas chromatographic analysis:
Trans 1-(2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl)-1-ethyl ketone 6%
Cis 1-(2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl)-1-ethyl ketone 1%
1-(2,6,6-trimethylammonium-2-tetrahydrobenzene-1-yl)-1-ethyl ketone 86%
1-(2,2-dimethyl-6-methylene radical-1-cyclohexyl)-1-ethyl ketone 2%
1-(2,6,6-trimethylammonium-1-tetrahydrobenzene-1-yl)-1-ethyl ketone 2%
Embodiment 2
1-in the presence of the catalyzer that obtains with Lewis acid (2,6,6-trimethylammonium-3-hexamethylene Alkene-1-yl)-isomerization of 1-ethyl ketone
20 ℃, under nitrogen protection, to (4.52 moles of trans 1-(2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl)-1-ethyl ketone; Trans/cis=94/5 is to 99/1, purity 〉=99%) in stir and add BF 3(AcOH) 2(the BF of 2.27 mmoles 3) and then add [Ru (COD) (methylallyl) 2] (2.27 mmole).The solution that obtains is heated to 130 ℃ and keep this temperature to stir 30 minutes under nitrogen protection.Afterwards, the mixture that obtains is cooled to 20 ℃ of mixtures (weight percent with final product calculates, and obtains by gas chromatographic analysis) that can obtain containing following material:
Trans 1-(2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl)-1-ethyl ketone 7%
Cis 1-(2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl)-1-ethyl ketone 1%
1-(2,6,6-trimethylammonium-2-tetrahydrobenzene-1-yl)-1-ethyl ketone 87%
1-(2,2-dimethyl-6-methylene radical-1-cyclohexyl)-1-ethyl ketone 2%
1-(2,6,6-trimethylammonium-1-tetrahydrobenzene-1-yl)-1-ethyl ketone is not observed
Embodiment 3
1-in the presence of the catalyzer that obtains with Lewis acid (2,6,6-trimethylammonium-3-hexamethylene Alkene-1-yl)-isomerization of 2-butylene-1-ketone
20 ℃, under nitrogen protection, to trans 1-(2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl)-2-butylene-1-ketone (25 grams; 130 mmoles; Trans: cis=98: 2, purity 〉=99%) the middle adding BF that stirs 3(AcOH) 2(0.65 mmole) and then add [Ru (COD) (methylallyl) 2] (0.65 mmole).The solution that obtains is heated to 130 ℃ and keep this temperature to stir 60 minutes under nitrogen protection.Afterwards, the mixture that obtains is cooled to 20 ℃ of mixtures (weight percent with final product calculates, and obtains by gas chromatographic analysis) that can obtain containing following material:
Trans 1-(2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl)-2-butylene-1-ketone 9%
1-(2,6,6-trimethylammonium-2-tetrahydrobenzene-1-yl)-2-butylene-1-ketone 86%
1-(2,2-dimethyl-6-methylene radical-1-cyclohexyl)-2-butylene-1-ketone 1%
1-(2,6,6-trimethylammonium-1-tetrahydrobenzene-1-yl)-2-butylene-1-ketone is not observed

Claims (17)

1. method turns to the mixture of the compound of the compound that contains at least a formula (II) and at least a formula (II ') with the substrate isomery shown in the formula (I),
Figure C2004800364030002C1
Each R wherein 1Simultaneously or represent hydrogen atom or methyl group and R independently 2Represent the C of hydrogen atom, straight or branched 1-4Alkyl or C 2-5The 1-alkenyl group;
Figure C2004800364030002C2
R wherein 1And R 2Have above-mentioned shown in identical implication;
Described method is to carry out in non-coordination or weak coordinate medium, under the condition that exists of inert environments catalyst neutralisation, and above-mentioned catalyzer is in non-coordination or weak coordinate medium and is obtained by the reaction between the following material in the inert environments:
A) formula [ruthenium (diene) (allyl group) 2], [ruthenium (dialkylene) 2], the ruthenium precursor of [ruthenium (tetraene) (alkene)] or [ruthenium (diene) (triolefin)]; With
B) protonic acid of formula HX, wherein X is weak coordination or non-coordinate negatively charged ion; Or formula B (R 3) 3Lewis acid, R wherein 3Represent fluoride or by 1 to 5 from halogen atom, methyl and CF 3The phenyl group that the group of selecting in the group replaces arbitrarily, perhaps formula FeX 3, FeX 2, AgX, AlY 3, FeY 3, FeY 2, SnY 2, SnY 4, AgY, AgY 2, SbY 5, AsY 5Or PY 5Lewis acid, X is to be the fluorine or chlorine atom as top defined group and Y;
The mol ratio of acid/ruthenium is 0.3 to 3.1.
2. according to the method for claim 1, it is characterized in that compound (I), (II) or (II ') are following formulas
Figure C2004800364030003C1
R wherein 1And R 2Have with implication identical shown in the claim 1 and asterisk and be meant that described compound is the form of optically active form.
3. according to the method for claim 2, it is characterized in that described substrate is (2E)-1-[(1S, 2R)-2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl]-2-butylene-1-ketone, (2E)-1-[(1S, 2S)-2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl]-2-butylene-1-ketone, 1-[(1S, 2R)-2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl]-1-ethyl ketone or 1-[(1S, 2S)-2,6,6-trimethylammonium-3-tetrahydrobenzene-1-yl]-the 1-ethyl ketone.
4. according to the method for claim 1, it is characterized in that described substrate is following formula (IV):
Figure C2004800364030003C2
R wherein 1And R 2Have and implication identical shown in the claim 1; And the compound that contains corresponding formula V and (V ') in the mixture that obtains,
Figure C2004800364030003C3
R wherein 1And R 2Have and implication identical shown in the claim 1.
5. according to the method for claim 4, it is characterized in that R 1Represent hydrogen atom and R 2Represent hydrogen atom or methyl or CH=CHCH 3Group.
6. according to the method for claim 1, it is characterized in that ruthenium precursor is the compound of following general formula:
I) [ruthenium (diene) (allyl group) 2], wherein " diene " representative encircles suffering-1,5-diene, norbornadiene or heptan-1, and the 4-diene, and " allyl group " represents 2-allyl group or 2-methylallyl;
Ii) [ruthenium (dialkylene) 2], wherein " dialkylene " represents pentadienyl, 2,4-dimethyl pentadiene base, 2,3,4-trimethylammonium pentadienyl, 2,4-two (tertiary butyl)-pentadienyl, 2,4-dimethyl-1-oxa-pentadienyl or 2,5-cyclooctadiene base or 2,5-cycloheptadiene base;
Iii) [ruthenium (diene) (triolefin)], wherein " diene " has above-mentioned identical implication and " triolefin " representative ring suffering-1,3,5-triolefin; Or
Iv) [ruthenium (tetraene) (alkene)], wherein " tetraene " representative encircles suffering-1,3,5, and 7-tetraene and " alkene " are represented cyclooctene or tetrahydrobenzene.
7. according to the method for claim 6, it is characterized in that ruthenium precursor is following complex compound: [Ru (ring suffering-1,5-diene) (2-methylallyl) 2], [Ru (ring hot-1,5-diene) (ring hot-1,3,5-triolefin)], [Ru (2,4-dimethyl pentadiene base) 2] or [Ru (2,4-dimethyl-1-oxa-pentadienyl) 2].
8. according to the method for claim 1, it is characterized in that X is ClO 4 -, R 4SO 3 -, R wherein 4Be chlorine or fluorine atom or C 1-C 8Fluoro-alkyl or fluorinated aryl group, BF 4 -, PF 6 -, SbCl 6 -, AsCl 6 -, SbF 6 -, AsF 6 -Or BR 4 -, wherein the R representative can be by 1 to 5 from halogen atom, methyl and CF 3The phenyl group that the group of selecting in the group replaces arbitrarily.
9. method according to Claim 8 is characterized in that X is BF 4 -, PF 6 -, C 6F 5SO 3 -, CF 3SO 3 -Or also have B[3,5-(CF 3) 2C 6H 4] 4 -
10. according to the method for claim 1, it is characterized in that sour HX is HBF 4Et 2O.
11., it is characterized in that Lewis acid is FeCl according to the method for claim 1 3, AlCl 3, SbF 5, AsF 5Or PF 5, AgF, Fe (CF 3SO 3) 3, AgBF 4, SnCl 2, BF 3, BMe 3, or BF 3With ether or carboxylic acid R 6 2O or R 7The adducts of COOH, wherein R 6Be C 1-C 5Alkyl group and R 7Be C 1-C 20Alkyl group.
12., it is characterized in that Lewis acid is BF according to the method for claim 11 3Or BF 3With Et 2O, Bu 2The adducts of O or AcOH.
13., it is characterized in that non-coordination or weak coordinate medium are chlorating hydrocarbon, saturated or undersaturated hydrocarbon, ether, ester, carboxylic acid, weak coordinate ketone or as the substrate of the defined formula of claim 1 (I), or their mixture according to the method for claim 1.
14., it is characterized in that used catalyst concentration is about 0.1 to 0.4 mole of % with respect to substrate according to the method for claim 1.
15. catalyzer that obtains by the reaction of following material:
A) formula [ruthenium (diene) (allyl group) 2], [ruthenium (dialkylene) 2], the ruthenium precursor of [ruthenium (tetraene) (alkene)] or [ruthenium (diene) (triolefin)]; With
B) formula B (R 3) 3Lewis acid, R wherein 3Represent fluoride or by 1 to 5 from halogen atom, methyl and CF 3The phenyl group that the group of selecting in the group replaces arbitrarily, perhaps formula FeX 3, FeX 2, AgX, AlY 3, FeY 3, FeY 2, SnY 2, SnY 4, AgY, AgY 2, SbY 5, AsY 5Or PY 5Lewis acid, X is to be the fluorine or chlorine atom as top defined group and Y;
The mol ratio of acid/ruthenium be 0.3 to 3.1 and this reaction be in non-coordination or weak coordinate medium He in the inert environments, to carry out.
16., it is characterized in that ruthenium precursor is as defined in claim 6 or 7 according to the catalyzer of claim 15.
17., it is characterized in that Lewis acid is BF according to the catalyzer of claim 15 or 16 3, BF 3Et 2O, BF 3Bu 2O or BF 3(AcOH) 2
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